US20120148743A1

US20120148743A1 - Method and apparatus for depositing led organic film

Info

Publication number: US20120148743A1
Application number: US13/359,434
Authority: US
Inventors: Vladimir Bulovic; Marc A. Baldo; Martin A. Schmidt; Valerie Gassend; Jianglong Chen
Original assignee: Massachusetts Institute of Technology
Current assignee: Massachusetts Institute of Technology
Priority date: 2004-11-19
Filing date: 2012-01-26
Publication date: 2012-06-14
Anticipated expiration: 2025-11-21
Also published as: US20110262624A1; US20060115585A1; US9005365B2; US9385322B2; US8128753B2

Abstract

In one embodiment the disclosure relates to an apparatus for depositing an organic material on a substrate, including a source heater for heating organic particles to form suspended organic particles; a transport stream for delivering the suspended organic particles to a discharge nozzle, the discharge nozzle having a plurality of micro-pores, the micro-pores providing a conduit for passage of the suspended organic particles; and a nozzle heater for pulsatingly heating the micro-pores nozzle to discharge the suspended organic particles from the discharge nozzle.

Description

This instant application is a continuation of U.S. Non-Provisional application Ser. No. 11/282,472 filed Nov. 21, 2005 and claims the filing-date priority to U.S. Provisional Application No. 60/629,312, filed Nov. 19, 2004.

BACKGROUND

The disclosure relates to a method and apparatus for depositing an organic film on a substrate. Manufacturing light emitting diode (LED) cell requires depositing of two thin organic films on a substrate and coupling each of the thin films to an electrode. Conventionally, the deposition step is carried out by evaporating the desired organic film on the substrate. The film thickness is a prime consideration. The layer thickness is about 100 nm and each layer is optimally deposited to an accuracy of about .+−0.10 nm. As a result, conventional apparatus form multiple layers on a substrate with each layer having a thickness of about 10 nm. A combination of these layers will form the overall film. Because the organic constituents of the LED are often suspended in a solvent, removing the solvent prior to depositing each layer is crucial. A small amount of solvent in one layer of deposited organic thin film can cause contamination and destruction of the adjacent layers. Conventional techniques have failed to address this deficiency.
Another consideration in depositing organic thin films of an LED device is placing the films precisely at the desired location. Conventional technologies use shadow masking to form LED films of desired configuration. The shadow masking techniques require placing a well-defined mask over a region of the substrate followed by depositing the film over the entire substrate. Once deposition is complete, the shadow mask is removed to expose the protected portions of the substrate. Since every deposition step starts by forming a shadow mask and ends with removing and discarding the mask, a drawback of shadow masking technique is inefficiency.

SUMMARY OF THE DISCLOSURE

In one embodiment the disclosure relates to an apparatus for depositing an organic material on a substrate, the apparatus comprising: a source heater for heating organic particles to form suspended organic particles; a transport stream for delivering the suspended organic particles to a discharge nozzle, the discharge nozzle having a plurality of micro-pores, the micro-pores providing a conduit for passage of the suspended organic particles; and a nozzle heater for pulsatingly heating the nozzle to discharge the suspended organic particles from the discharge nozzle.
According to another embodiment, the disclosure relates to a method for depositing a layer of substantially solvent-free organic material on a substrate, comprising heating the organic material to form a plurality of suspended organic particles; delivering the suspended organic particles to a discharge nozzle, the discharge nozzle having a plurality of micro-pores for receiving the suspended organic particles; and energizing the discharge nozzle to pulsatingly eject the suspended organic particles from the discharge nozzle. Organic particle may include an organic molecule or a molecular aggregate.
According to another embodiment, the disclosure relates to a method for depositing a layer of organic material on a substrate. The organic material may be suspended in solvent to provide crystal growth or to convert an amorphous organic structure into a crystalline structure. The method can include heating the organic material to form a plurality of suspended organic particles; delivering the suspended organic particles to a discharge nozzle, the discharge nozzle having a plurality of micro-pores for receiving the suspended organic particles; and energizing the discharge nozzle to pulsatingly eject the suspended organic particles from the discharge nozzle. Organic particle may include an organic molecule or a molecular aggregate.
According to still another embodiment, the disclosure relates to an apparatus for depositing an organic compound on a substrate comprising a chamber having a reservoir for receiving the organic compound, the chamber having an inlet and an outlet for receiving a transport gas; a discharge nozzle having a plurality of micro-porous conduits for receiving the organic compound delivered by the transport gas; and an energy source coupled to the discharge nozzle to provide pulsating energy adapted to discharge at least a portion of the organic compound from one of the micro-porous conduits to a substrate.
In yet another embodiment, an apparatus for depositing an organic compound comprises a chamber having a reservoir for housing the organic material dissolved in a solvent, the reservoir separated from the chamber through an orifice; a discharge nozzle defined by a plurality of micro-porous conduits for receiving the organic compound communicated from the reservoir; and an energy source coupled to the discharge nozzle providing pulsating energy for discharging at least a portion of the organic compound from one of the micro-porous conduits to a substrate; and a delivery path connecting the chamber and the nozzle. The organic compound may be substantially free of solvent. Alternatively, the organic compound may include in solvent. In a solvent-based system, the solvent discharge from the nozzle provides the added benefit of cooling the nozzle upon discharge.
In still another embodiment, a micro-porous nozzle for depositing an organic composition on a substrate includes a thermal source communicating energy to organic material interposed between the heater and a porous medium, the porous medium having an integrated mask formed thereon to define a deposition pattern.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a discharge apparatus for discharging organic compounds, or its mixture, according to one embodiment of the disclosure;

FIG. 2 is a schematic representation of a discharge apparatus for discharging organic compounds according to another embodiment of the disclosure;

FIG. 3 schematically illustrates a discharge nozzle according to one embodiment of the disclosure;

FIGS. 4A and 4B show an image printed according to one embodiment of the disclosure;

FIG. 5 is a photoluminescence image of a pattern printed by molecular jet printer system;

FIGS. 6A and 6B show the surface and the cross section, respectively, of a porous medium; and

FIGS. 7A and 7B illustrate a molecular jet printing apparatus according one embodiment of the disclosure in cross-sectional and top views, respectively.

DETAILED DESCRIPTION

In one embodiment, the disclosure relates to a method and apparatus for depositing a pure organic thin film, or a mixed organic film, or an organic thin film mixed with inorganic particles, or inorganic thin film on a substrate. Such films can be used, among others, in the design and construction of organic LED.
FIG. 1 is a schematic representation of a discharge apparatus for discharging organic compounds, or its mixture, according to one embodiment of the disclosure. Referring to FIG. 1, exemplary apparatus for deposing an organic material on a substrate includes housing 105 having discharge nozzle 125 at one end and a reservoir 107 at another end. Reservoir 107 may contain organic constituents required for forming an LED film. The organic constituent may be liquid or solid. Heat source 110 is provided to heat reservoir 107 and the content thereof. Heat source 110 can provide heating of about 100-700.degree. C.
Housing 105 may optionally include inlet 115 and outlet 120. The inlet and outlet can be defined by a flange adapted to receive a carrier gas (interchangeably, transport gas.) In one embodiment, the carrier gas is a inert gas such as nitrogen or argon. Delivery path 135 can be formed within housing 105 to guide the flow of the carrier gas. Thermal shields 160 may be positioned to deflect thermal radiation from hear source 110 to thereby protect discharge nozzle 125 and organic particles contained therein.
In the exemplary embodiment of FIG. 1, the discharge section includes discharge nozzle 125 and nozzle heater 130. Among others, the discharge nozzle can be formed from anodized porous aluminum oxide or porous silicon membranes or other solid membranes. Such material are capable of blocking organic material from escaping through the porous medium when the organic material is delivered onto the porous medium's surface. Discharge nozzle 125 includes rigid portions 141 separated by micro-pores 140. Micro-pores 140 block organic material from escaping through the medium until the medium is appropriately activated. Depending on the desired application, micro-pores 140 can provide conduits (or passages) in the order of micro- or nano-pores. In one embodiment, the pore size is in the range of about 5 nm-100 microns. In another embodiment pores are about 100 nm to about 10 microns. Nozzle heater 130 is positioned proximal to the discharge nozzle 125. When activated, nozzle heater 130 provides a pulse of energy, for example as heat, to discharge nozzle 125. The activation energy of the pulse dislodges organic material 109 contained within micro-pores 140.
In a method according to one embodiment of the disclosure, reservoir 107 is commissioned with organic material suitable for LED deposition. The organic material may be in liquid or solid form. Source heater 110 provides heat adequate to evaporate the organic material and form suspended particles 109. By engaging a carrier gas inlet 115, suspended particles 109 are transported through thermal shields 160 toward discharge nozzle 125. The carrier gas is directed to gas outlet 120 through delivery path 135. Particles 109 reaching discharge nozzle are lodged in micro-pores 130. Activating nozzle heater 130 to provide energy to discharge nozzle 125 can cause ejection of organic particles 109 from the discharge nozzle. Nozzle heater 130 can provide energy in cyclical pulses. The intensity and the duration of each pulse can be defined by a controller (not shown.) The activating energy can be thermal energy. A substrate can be positioned immediately adjacent to discharge nozzle 125 to receive the ejected organic particles. Applicants have discovered that the exemplary embodiment shown in FIG. 1 can form a think organic film on a substrate with great accuracy. The embodiment of FIG. 1 is also advantageous in that it can substantially reduce substrate heating, minimizes local clogging and provide the most efficient use of organic material.
FIG. 2 is a schematic representation of a discharge apparatus for discharging organic compounds according to another embodiment of the disclosure. Referring to FIG. 2, apparatus 200 is adapted for forming an organic film substantially free from solvent. Apparatus 200 includes reservoir 210 for receiving organic solution 215. In one embodiment, organic solution 215 contains organic material dissolved in a solvent. Thermal resistor 220 is positioned proximal to reservoir 210 to heat organic solution 215. Orifice 232 separates reservoir 210 from discharge nozzle 225. Discharge nozzle 225 comprises micro-pores 240 separated by rigid sections 241.
Because of the size of orifice 232, surface tension of organic solution prevents discharge of organic solution 215 from the reservoir until appropriately activated. Once thermal resistor 220 is activated, energy in the form of heat causes evaporation of droplet 235 within a chamber of apparatus 200. Solvents have a lower vapor pressure and evaporate rapidly. Once evaporates, organic compound within droplet 235 is transported to discharge nozzle 225. Discharge nozzle 225 receives the organic material 209 within micro-pores 240. The solvent can be recycled back to organic solution 215 or can be removed from the chamber (not shown). By activating nozzle heater 230, micro-pores 240 dislodge organic particles 209, thereby forming a film on an immediately adjacent substrate (not shown.) In one embodiment, nozzle heater 230 can be activated in a pulse-like manner to provide heat to discharge nozzle cyclically.
FIG. 3 schematically illustrates a discharge nozzle according to one embodiment of the disclosure. In FIG. 3, discharge nozzle 300 comprises heater 330, porous medium 340 and integrated mask 345. Heater 330 is communicates pulse energy in the form of heat to organic material 309 causing dislodge thereof from porous medium 340. Integrated mask 345 effectively masks portions of the porous medium from transmitting organic ink material 309. Consequently, a film forming on substrate 360 will define a negative image of the integrated mask.
Thus, in one embodiment, the particles can be discharged from the porous medium by receiving thermal energy from a proximal resistive heater, or a thermal radiation heater, or by electrostatic force pull out of the micro-porous, or by mechanical vibration.
FIGS. 4A and 4B show an image printed according to one embodiment of the disclosure. Specifically, FIG. 4 shows the printing result using the exemplary apparatus shown in FIG. 3. The ink material is Alq3 and was pre-coated on the backside of an anodized porous alumina disc. FIG. 4A shows the LED organic printed pattern under halogen illumination. FIG. 4B shows the photoluminescence image under UV illumination.
FIG. 5 is a photoluminescence image of a pattern printed by molecular jet printer system according to another embodiment of the disclosure. FIG. 5 was obtained by using the discharge nozzle shown in FIG. 3. The ink material was Alq3. The ink material was drop cast on the backside of anodized porous alumina disc.
FIGS. 6A and 6B show the surface and the cross section, respectively, of a porous medium. The porous medium can be used according to the principles disclosed herein with a discharge nozzle or as a part of a nozzle having an integrated mask (see FIG. 3.) FIG. 6A shows the surface of the porous medium. FIG. 6B shows a cross-section of the porous medium. FIG. 6A shows a scale of 1 μm and FIG. 6B has a scale of 2 μm.
FIGS. 7A and 7B illustrate a molecular jet printing apparatus according to an embodiment of the disclosure in cross-sectional and top views, respectively. Referring to FIG. 7A, printing apparatus 700 includes micro-heater 710 which can be used as a liquid delivery system. Wafer bonding layer 715 connects the liquid delivery system to nozzle section 720. Porous openings 730 are positioned at a discharge end of nozzle 720 and micro-heaters 740 are positioned adjacent to porous openings 730 to providing energy required to eject organic material or ink from nozzle 720. FIG. 7B shows a top view of the nozzle shown in FIG. 7A including porous openings 730 and heaters 740.
While the principles of the disclosure have been illustrated in relation to the exemplary embodiments shown herein, the principles of the disclosure are not limited thereto and include any modification, variation or permutation thereof.

Claims

1. An apparatus for depositing one more organic materials onto a substrate, comprising:

a source for providing organic material in substantially vapor form; wherein the source includes a collimating member proximate thereto, configured to collimate the vapor,

a substrate material positioned for receiving portions of the organic material,

a mask comprising a plurality of openings disposed between the source and substrate, and

a plurality of delivery paths extending from the source, through the plurality of openings, and to the substrate,

whereby portions of the organic material can be deposited on the substrate.

2. The apparatus of claim 1, wherein the source comprises an evaporation source.

3. The apparatus of claim 1, configured to operate in a relative vacuum.

4. The apparatus of claim 1, wherein the one or more organic materials define one or more respective solvent-based compositions.

5. An apparatus for depositing one or more organic materials onto a substrate, comprising:

a first substantially planar member, defining a plurality of columnar conduits, disposed along a first substantially planar region;

a second substantially planar member, defining a plurality of openings, disposed along a second substantially planar region; wherein the second planar region is adjacent and substantially parallel to the first planar region;

a source of an organic material adjacent and adapted for fluid communication with the first substantially planar member;

a thermal source configured to direct (a) a first portion of the organic material along a delivery path extending from the source, through the plurality of columnar conduits, through the plurality of openings, and onto the substrate, and (b) a second portion of the organic material from the source and onto a surface of the second substantially planar member;

whereby a film comprising the first portion of organic material can be formed on the substrate.

6. The apparatus of claim 5, configured to operate in a relative vacuum.

7. The apparatus of claim 6, wherein the plurality of columnar conduits comprises a plurality of micro-pores.

8. The apparatus of claim 6, wherein the second substantially planar member comprises a mask.

9. The apparatus of claim 5, wherein the one or more organic materials define one or more respective solvent-based compositions.

10. The apparatus of claim 5, further comprising a transport gas for delivering the one or more organic materials towards the first substantially planar member.

11. A method for depositing one or more organic materials onto a substrate, comprising:

forming a vapor comprising the one or more organic materials;

passing the vapor through a plurality of columnar conduits, whereby the vapor is substantially collimated upon exiting each of the conduits;

passing portions of the collimated vapor through a plurality of openings in a mask;

impinging other portions of the collimated vapor onto a surface of the mask;

forming a deposition pattern of the organic material on the substrate from the vapor portions that pass through the openings of the mask and reach the substrate.

12. A method for depositing one or more organic materials onto a substrate, comprising:

providing an apparatus comprising a source of an organic material, a substrate material positioned for receiving portions of the organic material, a collimating member disposed proximate the source, and a mask comprising a plurality of openings disposed between the source and substrate,

directing the organic material from the source such that portions of the organic material pass through openings of the collimating member in substantially collimated form,

passing portions of substantially collimated organic material emanating from the collimating member through respective openings of the mask, and impinging other portions of the organic material upon a surface of the mask such that the other portions are thereby blocked from passing onward toward the substrate, and

forming a film on the substrate comprising the portions of organic material passed through openings of the mask.